Preparation of Cu-Mn-I Solid Solution Thin Films and Control of Their p-type Transparent Conductive Properties

doi:10.15541/jim20250022

Abstract

Abstract: In the field of optoelectronic devices, p-type transparent semiconductor materials with controllable electrical properties hold significant application value. CuI, as a representative material, still faces considerable technical challenges in terms of preparation processes and doping control. This study successfully developed a new p-type transparent semiconductor material with adjustable electrical properties through manganese cation doping, offering a new approach for the advancement of transparent electronics. The Cu_1-_xMn_xI solid solution film, prepared via reactive magnetron sputtering, demonstrates unique performance advantages. First, the material can be fabricated at room temperature while maintaining excellent visible light transparency. Second, as the manganese doping concentration (x) increases, the grain size of the film gradually decreases, and pronounced crystal cluster aggregation is observed at higher doping concentrations. X-ray photoelectron spectroscopy analysis reveals that manganese ions in the film exist in a mixed valence state of Mn²⁺ and Mn³⁺. Electrical performance characterization shows that the resistivity of the film can be tuned over two orders of magnitude, ranging from 0.02 to 2.5 Ω·cm, while the hole carrier concentration remains stable at a high level of 10¹⁸-10¹⁹ cm^-³. Unlike the n-type doping behavior observed in traditional semiconductors, the introduction of high-valent manganese ions does not significantly affect the p-type conductivity of the material. This is likely due to the partially localized electronic state formed when manganese replaces cuprous ions. This discovery suggests that the hole conductivity of CuI semiconductors is not easily affected by high-valent manganese ion doping, enabling a wide range of compositional adjustments while maintaining stable p-type conductivity. This provides a valuable material basis for the development of CuI-based multifunctional transparent electronic devices.

Key words: Cu_1-_xMn_xI, transparent p-type semiconductor, controllable p-type resistivity

CLC Number:

TQ174

WANG Liangjun, OUYANG Yuzhao, ZHAO Junliang, YANG Chang. Preparation of Cu-Mn-I Solid Solution Thin Films and Control of Their p-type Transparent Conductive Properties[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20250022.

References

[1] LIU A, ZHU H H, KIM M G,et al. Engineering copper iodide (CuI) for multifunctional p-type Transparent semiconductors and conductors. Advanced Science, 2021, 8(14): 2100546.
[2] THOMAS G.Invisible circuits.Nature, 1997, 389(6654): 907.
[3] KAWAZOE H, YASUKAWA M, HYODO H,et al. P-type electrical conduction in transparent thin films of CuAlO₂. Nature, 1997, 389(6654): 939.
[4] UEDA K, HASE T, YANAGI H,et al. Epitaxial growth of transparent p-type conducting CuGaO₂ thin films on sapphire (001) substrates by pulsed laser deposition. Journal of Applied Physics, 2001, 89(3): 1790.
[5] YANAGI H, HASE T, IBUKI S,et al. Bipolarity in electrical conduction of transparent oxide semiconductor CuInO₂ with delafossite structure. Applied Physics Letters, 2001, 78(11): 1583.
[6] KUDO A, YANAGI H, HOSONO H,et al. SrCu₂O₂ A p-type conductive oxide with wide band gap. Applied Physics Letters, 1998, 73(2): 220.
[7] RAGHUPATHY R K M, KÜHNE T D, FELSER C,et al. Rational design of transparent p-type conducting non-oxide materials from high-throughput calculations. Journal of Materials Chemistry C, 2018, 6(3): 541.
[8] YANG C, KNEIß M, LORENZ M,et al. Room-temperature synthesized copper iodide thin film as degenerate p-type transparent conductor with a boosted figure of merit. Proceedings of the National Academy of Sciences, 2016, 113(46): 12929.
[9] GENG F J, WANG L J, STRALKA,et al.(111)-oriented growth and acceptor doping of transparent conductive CuI:S thin films by spin coating and radio frequency-sputtering. Advanced Engineering Materials, 2023, 25(11): 2201666.
[10] YANG J L, JIANG X L, RUAN S Y,et al. Highly weak-light sensitive and dual-band switchable photodetector based on CuI/Si unilateral heterojunction. Journal of Inorganic Materials, 2024, 39(9): 1063.
[11] GRUNDMANN M, SCHEIN F-L, LORENZ M,et al. Cuprous iodide-a p-type transparent semiconductor: history and novel applications. Physica Status Solidi (a), 2013, 210(9): 1671.
[12] GRUNDMANN M. Karl Bädeker (1877-1914) and the discovery of transparent conductive materials.Physica Status Solidi (a) - Applications and Materials Science, 2015, 212(7): 1409.
[13] CHEN D, WANG Y, LIN Z,et al. Growth strategy and physical properties of the high mobility p-type CuI crystal. Crystal Growth & Design, 2010, 10(5): 2057.
[14] JUN T, KIM J, SASASE M,et al. Material design of p-type transparent amorphous semiconductor, Cu-Sn-I. Advance Materials, 2018, 30(12): 1706573.
[15] YANG C, SOUCHAY D, KNEIß M, et al. Transparent flexible thermoelectric material based on non-toxic earth-abundant p-type copper iodide thin film. Nature Communications, 2017, 8(1): 16076.
[16] ZENG G X, DOU W, GAN X M,et al. Low-voltage solution-processed Na_xCu₁-_xI thin-film transistors for mimicking synaptic plasticity. Applied Physical Letters, 2024, 124(12): 123508.
[17] JIANG G G, DOU W, GAN X M, et al. Low-voltage solution-processed P-type Mg-doped CuI thin film transistors with NAND logic function. Applied Physical Letters, 2023, 122(21): 213501.
[18] GHAZAL N, MADKOUR M, NAZEER A A, et al. Electrochemical capacitive performance of thermally evaporated Al-doped CuI thin films. RSC Advance, 2021, 11(62): 39262-39269.
[19] MIRZA A S, VISHAL B, DALLY P,et al. Cs‐doped and Cs‐S Co-doped CuI p‐type transparent semiconductors with enhanced conductivity. Advanced Functional Materials, 2024, 34(30): 2316144.
[20] MUDE N N, BUKKE R N, JIANG J.Transparent, P-channel CuISn thin-film transistor with field effect mobility of 45 cm²·V^-1·s^-1 and Excellent Bias Stability.Advanced Materials Technologies, 2022, 7(8): 2101434.
[21] TAREY R D, RAJU T A.A method for the deposition of transparent conducting thin films of tin oxide.Thin Solid Films, 1985, 128(3/4): 181.
[22] LIU A, ZHU H H, W T PARK,et al. Room-temperature solution-synthesized p-type copper(I) iodide semiconductors for transparent thin-film transistors and complementary electronics. Advanced Materials, 2018, 30(34): 1802379.
[23] STRELCHUNK V, KOLOMYS O, RARATA S,et al. Raman submicron spatial mapping of individual Mn-doped ZnO nanorods. Nano Epress, 2017, 12: 1.
[24] ZI M, LI J, ZHANG Z C,et al. Effect of deposition temperature on transparent conductive properties of γ-CuI film prepared by vacuum thermal evaporation. Physica Status Solidi (a), 2015, 212(7): 1466.
[25] SUNG S Y, KIM S Y, JO K M, et al. Fabrication of p-channel thin-film transistors using CuO active layers deposited at low temperature. Applied Physical Letters, 2010, 97(22): 222109.
[26] KYKYNESHI R, MCINTYRE D H, TATE J,et al. Electrical and optical properties of epitaxial transparent conductive BaCuTeF thin films deposited by pulsed laser deposition. Solid State Sciences, 2008, 10(7): 921.
[27] ZAKUTAYEV A, MCINTYRE D H, SCHNEIDER G,et al. Tunable properties of wide-band gap p-type BaCu(Ch₁-_xCh_x′)F (Ch=S, Se, Te) thin-film solid solutions. Thin Solid Films, 2010, 518(19): 5494.
[28] YANG C, KNEIß M, SCHEIN F-L, et al. Room-temperature domain-epitaxy of copper iodide thin films for transparent CuI/ZnO heterojunctions with high rectification ratios larger than 10⁹. Scientific Reports, 2016, 6(1): 21937.
[29] YANG C, ROSE E, YU W L,et al. Controllable growth of copper iodide for high-mobility thin films and self-assembled microcrystals. ACS Applied Electronic Materials, 2020, 2(11): 3627.